Detergent compound and method for preparing the same



Patented June 1-2, 1934 nErEaGEN'r COMPOUND AND rm'rnon Eon PREPARING 'rnE sum Ernest F. Drew, New York, N. Y.

No Drawing. Application September 14, 1928.

Serial No. 306,095

10 Claims.

My invention relates to processes for the treatment of waste liquors, from sulfonation of esteroils, such as animal and vegetable fats .or-oils,'=

naturally occurring glycerides, or other esters of fatty acids, and to a new composition of matter obtained by such processes (all of which sub-- stances are included in the nous materials).

A primary objectis to provide a process that can be expeditiously executed at small expense for utilizing in industry rather than wasting liquors of the above type.

Another object is to provide, more particularly by the utilization of waste liquors of the above type, a compound for laundry purposes, which expression oleagihas a detergent action practically equal to that of caustic soda, which emulsifies oils and greases to a high degree, which is more easily soluble in water than ordinary sodium carbonate, and

which, accordingly, permits considerable saving of soap or soap solutions, which rinses out easily and leaves the fabric uninjured and whiter and cleaner than do ordinary soap liquors.

Another object is to provide a composition of the above type, which is valuable 7 in the textile industry for kier boiling and eliminates the use of so-called kier assistants, which is useful in wool scouring or the cleansing of rayon fabrics before dyeing, and the use of which in every case results'in a white product of soft texture.

Another object is-to provide a product of the above type which inherently has a delicate bleaching action upon fabric treated thereby, without the addition of special bleaching agencies of any kind.

The treatment of common castor oil with sulfuric acid in the preparation of Turkey red oil is a typical example of oil sulfonation. While little is actually known of the precise character of the chemical reactions in this operation, uniform results depend on a strict control of certain factors, such as kind and exact quality of oil, quantity and strength of acid, temperature, time of s ulfonation, character and degree of neutralization, amount of-salting, etc.

Upon completion of sulfonation, it is common practice to facilitate the separation ofthe sulfonated oil from the excess sulfuric acid, by washing and the addition of salt (e. g. Glaubers salt) to the wash, water. The resulting lower aqueous layer is withdrawn. The supernatant layer of sulfonated oil may be further washed or treated, but it is with the wash water which is called waste liquor (preferably with? this first withdrawn layer of wash water) containing most of the sulfuricacid and the Glaubers or other salts and the glycerin which may have been produced by hydrolization, as well as other products of varying quantity and compositiom'that my invention particularly concerns itself.

It has been proposed to treat this waste liquor for the recovery of glycerin, but so far no commercially useful process of glycerol recovery has been devised, because until after neutralization; distilling is impractical and the cost of neutralizing with anything but lime has been prohibitive,

as, until now there has been no use for the liquor after removal of the glycerol. As a matter of commercial fact, these waste liquors" have heretofore been exactly what their name implies, an objectionable waste in which the free 7 acid has tobe killed with lime, making a disagreeable sludge which, even, then frequently contaminates the streams and constitutes a public nuisance.

One step in vrny process is the complete neutralization with soda, potash, magnesia or. the like, rather than with the -cheaper and less soluble lime. All the acid compounds which may occur in the waste liquor, including the sulfuric acid are thereby preferably neutralized to form soluble salts. This step may be carried out byitself with a certain degree of commercial advantage and utility for the recovery of glycerol or in order to facilitate transportation of the resulting product.

It is the valuemf the product, obtained by my' invention from the waste liquors, which renders feasible the use of the more expensive neutralizing agency, which latter presents the additional advantage, as above noted, .of facilitating the recovery of the glycerol.

Another step in the process consists in the admixture of this neutralized product, either immediately, or after distilling and transportation, with a washing material which may advantageously be an excess of the neutralizing material, as, for example, soda or, the like.

A third step in the process which I find in come cases advantageous though not indispensable, is the admixture of the neutralized material including the added washing material,

with a modifying, softening, solvent or degreasing material such as mineral oil or otherv organic solvent. g

The proportions of materials to be added, de-

pend somewhat on the choice of oil and the quality of the particular lot of oil, and also on conditions of sulfonation. I will give one typical example that will enable anyone skilled in the art to carry out my process for these particular conditions and, in the light of which, he may know how to obtain the best results from the particular waste liquor at hand and soda. ash or equivalent agent.

tating apparatus adapted to maintain the temperature below 35 C. The acid may be added gradually at the rate of two pounds per minute and then agitation of the batch continued for a period of 12 hours. At the expiration of this time the reaction is substantially completed. The batch is then diluted with an equal volume of water. The water used for this purpose is preferably substantially saturated with Glaubers salt, to assist in separation, this saturation being secured by the addition of one pound of Glaubers salt per gallon of dilution water used, or the salt may be added after dilution. Then the batch is allowed to settle and the lower aqueous layer or waste liquor .is drawn off, said liquor vcontaining the great bulk of the acid used in the-sulfonation and substantially all of the glycerol that has been liberated. The upper layer may, if desired, be further washed with water, preferably containing salt, and this wash water used (with or without concentration) in conjunction with the main waste liquor without departing from my invention, but for simplicity, the description will be confined to the specific steps of the process utilizing only the main waste liquor.

According to my process, the waste liquor is now neutralized by the addition per gallon of about two pounds of alkali, preferably soda ash. Potash could, of course, be used with greater expense, or caustic soda, as well as magnesia, might be used in place of some or all of the ash required during this portion of the operation. The resultant material forms the preliminary product of my invention and may be shipped, preferably after concentration by evaporation, or, it may be utilized as such if prepared near the place of ultimate use.

From this, it is now practical to recover at least a portion of the glycerol, if desired, by steam distillation during evaporation, but this forms no necessary part. of my process. Nor is the presence or the absence of glycerol in general material to my novel product A just described, though for certain purposes, I prefer to have some glycerol present.

While product A'above described, gives satisfactory results, experience has shown that it is preferable to add an excess of'alkali. This may be added to the preliminary product Aafter shipment, but it is preferably added at the time of substantial neutralization and is preferably an excess of the neutralizing agent. The two steps of neutralizing and adding washing compounds, may be performed by the direct action of the waste liquor on an excess of About seventyfive parts of sodium carbonate in the form of soda/ash are preferably mixed with twenty{ five parts by weight of wash liquor. It is quite practical merely to sprinkle the waste liquor on the large excess of soda while agitating the latter and subsequently to mix the batch thoroughly and regrind the more or less caked and lumpy mass produced by the formation of crystal soda therein. This material constitutes my product B. Special drying of the product is not required but may be resorted to without serious detriment. From the above specifica tions of ingredients, it is evident that only a small proportion of the soda ash in my product B has served for neutralizingthe .waste liquor, the rest being converted into" a special solid washing compound by the action of-the neutralized waste liquor thereon.

The dry product obtained as above explained, is found to be more easily soluble in water than the ordinary soda ash and to have far greater cleansing power.

As above indicated any of a wide variety of alkalis or bases could be used for neutralizing the acids in the waste liquor and the additional base in the form of a washing compound could be added. concurrently with the neutralization or after the'neutralization has been completed. In certain of the claims the neutralizing base is recited as an element and the washing compound as a distinct element, it being understood that regardless whether the same chemical is used for neutralization and as the added washing compound or whether differentchemicals are used for these purposes, the term washing compound as thus recited in the claims refers to the alkali in excess of that used for neutralization.

My product B has marked wetting out properties equalled only by caustic soda solutions. The strong detergent action is substantially as satisfactory as that of caustic soda but my product, unlike caustic soda, appears to have no harsh action on the textile fibers. My product is especially useful in laundering and permits on the one hand a great saving in soap solution and on the other, affords a solution which rinses out easily, leaving the material whiter and cleaner than do ordinary soap liquors. These properties render my product valuable also in the textile industries for kier boiling, because it will partially or wholly displace caustic alkali and eliminate other forms of so-called kier. assistants, at the same time, producing whiter goods having a softer texture. My product is particularly advantageous in the treatment of delicate fibers, as in wool scouring, or the cleansing of rayon fabrics before dyeing, and has proven in many ways superior to the so-called modified alkalies.

The chemical and physical actions that occur in the action of my product are not clearly understood by me and I have, therefore, advanced a tentative theory by which this action may be explained. This theory may be subject to modification and correction and I donot wish to be bound thereby.

The great and easy solubility of my product B appears to be due tothe fact that most of the soda ash is transformed to a mono-hydrated carbonate which has marked wetting out properties. The special high detergent action appears to be due as below more fully explained, to the impurities or complex compounds resulting as by-products left over in the waste liquor from the sulfonation.

In the sulfonation of castor oil, for instance, notwithstanding the care taken in salting out,

amounts of the sulfonation product invariably remain in the waste liquor, such portion being, of course, more soluble in water than the bulk of the reaction mass. These sulfonation products in the waste liquor are even soluble in saline solutions and do not easily decompose, resisting the action even of strong mineral acids. It has been found that wash liquors with an acidity of 25 per cent may be subjected to prolonged boiling. without decomposition of the small amounts of these resistantoils.

Apparently, these highly soluble salts of sulfonic acids posses the property of emulsifying oilsand greases to a higher degree than any other form of sulfonic acid salt. Thus, the

in removing by solution, oil and grease from fabric or stock being laundered or cleaned.

In typical cases, the waste liquor of ester oil sulfonation includes from 6 to 12 percent of sulfuric acid; '7 to 15 per cent of Glaubers salt; 1 to 4 per cent of glycerine and 1 to 5 per cent of water-soluble sulfonated oils. The waste liquor also includes smaller amounts of sulfurous acid.

. called water soluble or colloidally dispersed oils, and I call them hereinafter-soluble oils-. While these oils might not become readily dispersed in ordinary aqueous solutions, the

presence of the small proportion of soluble sulfonation product from the waste liquor, serves as an emulsifying or dispersing agent for the added soluble oils, which in my final product C act together with the sulfonation product as a superior degreasing agency.

One satisfactory way of obtaining and adding such dispersions is to treat the oil desired to be incorporated, with more or less of the waste liquor in the usual emulsifying apparatus, whereupon the oil or other solvent will generally-be so highly dispersed as to become apparently soluble in the waste liquor. The resultingdispersion is then added -to the mixture, preferably to the neutralizing alkali either before, during or after complete neutralization oi the liquor. A portion of such liquor may be separated from the rest and used as a medium for the solubilizing or emulsifying of the organic solvent which is therewith to be added as part of the final compound.

The sulfurous acid present in the wash liquors even after treatment acts as a bleaching agency and contributes to the valuable result.

It will thus be seen that there is herein de scribed a composition and method of preparing the same, in which theseveral features of this invention are embodied, and which composition attains the various objects of the invention and is well suited to meet'the requirements'of practical use.

As many changes could be made in the above composition and many apparently widely different embodiments of this invention could be made without departing from the scope thereof, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

Having thus described my invention, what I claim as new and desire to secure by Letters- Patent of the United States is:

1. In the preparation of a detergent composition, the process of utilizing waste liquors of furous acid), which comprises mixing therewith suificient alkaline compound of an alkali metal to neutralize the acids in the waste liquor, said compound being of a character to form salts with said acids that are highly soluble in water.

2. In the preparation of a detergent composi-- tion, the process of utilizing waste liquors of sulfonation of a higher fatty acid glycerine, which comprises mixing therewith sufficient soda ash to neutralize the acids in the waste liquor, and to form salts with saidacids that are highly soluble in water, said soda ash being added in quantity greater than that needed for neutralization whereby to afford an excess serving as a washing compound.

3. In the preparation of a detergent composition, the process of utilizing waste liquors ofester-oil sulfonation, which comprises mixing therewith sufficient soda ash to neutralize the acids in the waste liquor, and to form salts with said acids that are highly soluble in water,

mixing therewith soda ash in quantity greater than that used for neutralization, and also adding a small proportion of a soluble oil.

4. In the preparation of a detergent composition, the process of utilizing waste liquors of ester-oil sulfonation (which waste liquors include water, sulphuric acids, Glaubers salt, glycerine and minor quantities of water-soluble sulfonated oils, salts of sulfonic acid and sulfurous acid), which comprises mixing therewith a suflicient quantity of soda ash to neutralize the acids in said liquors.

5. In the preparation of a detergent composition, the process of utilizing waste liquors of ester-oil sulfonation (which waste liquors include water, sulphuric acids, Glaubers salt, glycerine and minor quantities of water-soluble sulfonated oils, salts o sulfonic acid and sulfurous acid), which comprises mixing therewith a quantity of soda ash greatly in excess of that required to neutralize the acids in the liquor.

6. In the preparation of a detergent composition, the process of utilizing waste liquors of ester-oil sulfonation, which comprises mixing therewith a quantity of soda ash greatly in excess of that required to neutralize the acids in the liquor, adding a small proportion of a soluble oil and grinding the resulting product.

7. A detergent composition including the waste liquors of ester-oil sulfonation, soda ash inquantity at least suflicient to neutralize the acids in the waste liquor and also including a small proportion of a soluble oil."

- 8. A detergent composition essentially composed of the waste liquors of castor oil sulfonation (which waste liquors include water, sulphuric acids, Glaubers salt, glycerine, and minor quantities of water-soluble sulfonated oils, salts of sulfonic acid and sulfurous acid), said composition including a quantity of soda ash in excess of that required to neutralize the acids in thk liquor.

9. A detergent composition essentially composed of the waste liquors from the sulfonation of an -oleaginous' material which composition includes a quantity of soda ash in excess of that required to neutralize the acids in the liquor. j

10. A detergent composition comprising the waste liquors of ester-oil sulfonation and about 300% soda ash andabout 5% of a soluble oil.

' ERNEST F. DREW. 

